Treatment of hydrocarbons



Patented Oct. 9, 1945 [UNITED STATES PATEN r OFFICE Walter A. Schulze, Bartlesville, Okla, assignor to Phillips Petroleum Delaware No Drawing.

sponding residue, from mixtures produced by the thermal or catalytic treatment of petroleum fractions or hydrocarbon stocks from any source. 7

In a still more specific sense this invention concerns the purification of said components of hydrocarbon mixtures subsequent to chemical absorption treatment for the segregation of diolefins and prior to further processing in which the impurities so removed would be detrimental.

Various processes for the production of diolefins and particularly of butadiene have been proposed.

These include the thermal cracking of petroleum fractions and higher molecular weight hydrocarbons of aliphatic or cyclic nature as well as the catalytic dehydrogenation of parafllns and/or oleflns of the same number of carbon atoms. Such processes involve the production and segregation of hydrocarbon mixtures which may contain, in addition to the desired diolefins, paraiiins, monooleflns and other unsaturatesof the same or a smaller nuniber of carbon atoms and often of approximately the same boiling range.

2 of the periodic system and particularly of so-' lutions of cuprous halides. Such cuprous salt solutions function through the formation of addi- Company, a corporation of Application September 3, 1940, Serial No. 355,257 a 7 Claims. (or. 260-680 sible to accomplish diolefin absorption and recovery by means of solid-type reagents comprising adsorbent carriers impregnated with suitable metal'salts and/or solutions thereof which 'produce and retain the diolefin addition compound during contact with hydrocarbon fluids. In processes utilizing such solid reagents as described in copending application, Serial No. 354,086, filed August 24, -1940,the hydrocarbon may be in either liquid or vapor phase although liquid phase operation is preferred because of'distinct advantages regarding operating flexibility and costs and the size of plant equipment.

tion compounds with unsaturated hydrocarbons" according to the following proposed eqations:

C Hu-l 011101: ---0 Gulch-0,112 Diolefln Guprous Diolefin addition I chloride compound 0.11, cuici, omen-on...

Monoolefin cuprous Oleiin add ition chloride compound The described methods of. absorbing unsaturates by-the use of cuprous halide solutions have been directed to treating gaseous hydrocarbonmixtures. More recently, it has been found ms- In'liquid phase absorption of unsaturates with cuprous halide solutions or -with solid cuprous halide reagents, it has been found that the abovementioned olefin and diolefin addition compounds have a definite sol ility in the hydrocarbon phase, depending on, he temperature of absorption and the composition of the hydrocarbon liquid. Apparently under the conditions favorable to the formation of solid diolefin addition compounds either or both of the addition products are retained in solution to some extent in the. liquid residuum and carried away from the cuprous halide reagent. In certain cases C4 hydrocarbon li ids after passage over acuprous chloride rea ent for-the removal of butadiene have shown appreciable amounts of copper salt residue on evaporation.

Coppercontamination as a result of the chemical separation process is extremely undesirable since it interferes with subsequent treatment of both the diolefin extract and the residuum. This is particularly true of those cyclic processes wherein the residuum from the diolefin extraction step is recycled for further conversion and production of diolefins. For example, themesence of copper in a butene-butane stock being recycled to a thermal or catalytic conversion operation to produce butadiene cannot be tolerated because of the catalytic effect of the copper on decomposition and polymerization reactions with consequent loss of valuable charging stock.

.The undesirable consequences of copper contamination' are also extended to those processes in whichcuprous halide reagents are used to segregate ,mono-olefins from paraffin-olefin hydrocarbon mixtures. Thus in processes fOr'the separation of-butenes from butene-butane mixtures copper compounds may be retained by the butan residuum from the separation p ocess and ex erfzarmful efiects in further dehy ogenation vo conversion 01' the parafllnic material.

operations except in cases or mixed phase de-- sorption or of the use of a liquid desorption agent.

The exact nature of the copper compounds'retained by hydrocarbon liquids following contact with cuprous salt reagents under the above-mentioned conditions is not known. It is assumed that both the olefin and diolefin addition compounds are present although the former may predominate on the basis of greater overall solubility in various solvents. The types of copper com- Pounds are limited to those formed with unsaturated hydrocarbons since no other salt-forming components are present in the hydrocarbon liquids undergoing treatment. l

I have now discovered a method of purification of hydrocarbon liquids of the type described sub- 'sequent to treatment with cuprous halide reagents whereby the retained copper compounds are removed and the harmful after-effects of copper contamination are eliminated. My method of purification. depends on the, conversion of soluble unsaturated hydrocarbon-cuprous halide compounds to insoluble inorganic copper salts which are removedv from the purified hydrocarbon liquid,

I have found that when the liquid hydrocarbon residuum from treatment with a cuprous halide reagent is intimately contactedwith an aqueous solution of aninorganic'compound the anion of which is capable of forming a water-insoluble copper salt that the cuprous halide addition comwhich have no reactivity toward hydrocarbons.

To secure satisfactory water solubility I may use the stable, non-volatile compounds of sodium, potassium and ammonium. although compounds of the alkaline earth metals and zinc and magnesium may be used for certain solutions if the water-solubility or the specific compounds is satisfactory. v

Theanions which are useful in forming waterinsoluble copper salts are sulfide, hydroxide, carbonate, phosphate and silicate. These anions;

may be present alone or in certain combinationssuch as sulfide and hydroxide which I have found to prevent the inclusion of ions that are mutually precipitatable in aqueous solution or which react together to form unstable or volatile products apt to contaminate the hydrocarbon liquid.

- Intimate contact between the hydrocarbon liquid containing unsaturated hydrocarboncuprous halide addition compounds and the aqueous reagent solution may be obtained by any suitable means such as mixing in a centrifugal pump or the like, spraying one liquid in atomized form through the other, or by passing the liquids counter-current to each other in a packed column or the like. Any mixing device which ailfords sufficient contact to insure rapid reaction between the two immiscible phases is satisfactory.

The temperatures which are suitable for the operation of my process are ordinary atmospheric temperatures of 40 to 110 F. Temperature is not critical as long as the aqueous reagent solution is not frozen or dissolved saltsare not precipitated, although higher temperatures are favorable to rapid reaction. a

The pressure required by my process are low superatmospheric pressures in the range of to 500 pounds gage. Suflicient pressure is fillnished to maintain the hydrocarbon in liquid phase at treating temperatures.

The time of contact may be quite short with extreme intimacy oi mixing. Thus, by mixing the hydrocarbon liquid and aqueous solution in 1:1 volume ratio into a temporary emulsion of very fine droplets, the reaction is quickly completed and on separation of the emulsion, the hydrocarbon is satisfactorily purified. I 7

The hydrocarbon liquids which are treated according to the terms of my invention are the prodnets of convertive reactions conducted under severe conditions for producing a high degree of unsaturation. Said liquids are of closely regulated composition and the control of composition,

fractionation and conversion are designed to promote high yields and eflicient utilization of raw materials. Under these conditions, impurities oi the nature of sulfur, nitrogen and oxygen compounds are substantially absent from the raw materials, or are removed during or subsequent to the convertivereactions. In catalytic dehyespecially eilective. All-are supplied in water so-- lutions by so-called strong inorganic bases or by the salts of strong bases and weak ,noneoxidizing acids which produce alkaline solutions by hydrolysis.

drogenation and thermal cracking at temperatures above 1000 F. for example; sulfur compounds are converted to hydrogen sulfide and removed from the hydrocarbon vapors prior to the segregation of stocks for the extraction of dioleflns. Oxygen compounds, if present, are similarly removed by the reduction in the hydrogen atmosphere of the convertive reactions. Organic nitrogen impurities are totally absent. Thus, the

stocks to be purified following the extraction of diolefins contain no compounds capable of combining with copper except the unsaturated hydrocarbons.

The following examples will serve to illustrate specific solution .preparations and the use of these solutions for the puriflcationof low-boiling hydrocarbon liquids. I

- 1 Example! x A butene-butane stock was catalytically dehydrogenated and the eilluent vapors were deethanized and condensed. The resulting Ca C4 liquid was cooled to a lowtemperaturc and passed over a solid reagent consisting of an adsorbentcarrier impregnated with cuprous chloride for the absorption of butadiene. olefin-:free residuum from this treatment which was recycle dehydrogenation'ieed stock' contained- The substantially diaseasso an appreciable amount of dissolved copper in the form of the unsaturated hydrocarbon addition.

compounds. The recycle material was passed to a mixing chamber for contact with a solution of.

per cent by weight of sodium sulfide and 5 per cent by weight of sodium hydroxide.

The hydrocarbon eflluent from the mixing I chamber was settled free of aqueous solution and Ezample II have illustrated theinvention and described several specific applications for obtaining the desired results, other modifications will be obvious to those skilled in the art according to the principles outlined. Therefore, the scope of the invention is limited only by the appended claims.

I claim:

1. In' a process for the production of butadiene which comprises dehydrogenatingbutane to produce butenes and butadiene, extracting the butadiene from the dehydrogenated liquid by means of a cuprous halide reagent and recycling the residuum from the cuproushalide treatment for further dehydrogenation, the step of purifying Thehydrocarbon liquid of Example I was.

washed with a solution oi sodium phosphate con- I taining 10 per cent by weight of the compound.

The washed and settled hydrocarbon gave no trace of copper salt residue on evaporation, and the purified stock was further dehydrogenated with a good yield of butadiene.

Similar results were obtained using aqueous solutions containing 10 per cent by weight of sodium carbonate and 5 per cent by weight of sodium silicate respectively.

Example III A C4 hydrocarbon liquid "consisting ofbutadiene; butenes and n-butane was contacted with a solution of cuprous-chloride in an immiscible solvent. The -solid butadiene-cuprous chloride addition productwas removed, and the butenebutane liquid was separated from the cuprous chloride reagent for further dehydrogenation.

This butane-butane liquid contained appreciable amounts of dissolved copper and was washed with 'a solution of 25 percent sodium hydroxide.

The aqueous solution was separated and the puri-. fled C4 liquid gave no copper residue on evaporation, whereupon it was returned to a dehydrogenation operation for the production of further butadiene.

When a water-soluble sulfide was added to'the" caustic solution, copper sulfide was precipitated in the aqueous solution following contact with the C4 liquid.

Example IV Nebutane was dehydrogenated to produce butenes and the eiiluents were, condensed and freed of light gases. The liquid butene-butane mixture sodium sulfide solution containing 5 per cent by weight of eachsalt, and after washing and settling wasfree of copper. This purified material was then recycled for further dehydrogenationwithsatisiactoryresults. v

While the foregoing disclosure and examples said residuum prior torecycling by treatmentwith an aqueous solutionot an alkaline-reacting non-oxidizing inorganic compound the anion of which forms a water-insolublecopper salt.

2. The process of claim 1 in which the inorganic compound comprises a water-soluble inorganic sulfide.

3. The process of claim 1 in which the inorganic compound comprises a water-soluble phosphate.

4. The process of claim 1 in which the inorganic compound comprises a water-soluble silicate.

was then contacted with a solution containing 'was washed with an aqueous sodium carbonatesolution comprises an alkali 5. A process for the manufacture of diolefins which comprises converting a hydrocarbon feed at least partially to diolefins in a conversion step, passing a low-boiling hydrocarbon liquid derived from the efiluent and comprising the diolefins so produced in contact'with a reagent in the form of, a solid adsorbent carrier impregnated with a cuprous halide under such conditions that substantially all of said diolefins are retained by said reagent in the form of an addition compound with said cuprous halide, removing the substantially diolefin-iree liquid residuum, purifying said liquid residuum by treating same with an aqueous solution of an alkaline-reacting water-soluble inorganic compound the anion of which forms a water-insoluble copper salt, and recycling the so purified residuum to said conversion step for further conversion to said diolefins.

6. A process for the recovery of diolefins from a liquid'hydrocarbon stream. comprising diolefins and other hydrocarbons which comprises contact.

ing said stream in liquid phase and substantially free from sulfur compounds with a cuprous halide reagent under conditions such that substantially all'of said diolefin combines with said cuprous halide to form an essentially insoluble ad-:

dltion. compound, separating the substantially diolefln-free liquid residuumfrom the reagent, said residuum containing an appreciable amount 01' dissolved copper in the form of unsaturated hydrocarbon-cuprous halide addition compounds,- and intimately contactingsaid residuum directa 1y with an aqueous solution of an alkaline-reacting water-soluble inorganic compound the union of which forms a water insoluble copper compound to thereby remove copper irom said residuum. q

7. The process of claim 1 in which said aqueous metal sulfide and an alkali metal hydroxide. A

-wan'raaascnorzn.. 

